Production of acetal derivatized hydroxyl aromatic polymers and their use in radiation sensitive formulations

ABSTRACT

The present invention provides a process for generating mixed acetal polymers by reacting a hydroxyl containing polymer or monomer with vinyl ether and alcohol in the presence of an acid catalyst. The process of this invention provides a new class of polymers based on mixed acetals which are prepared in-situ with one reaction. The mixed acetal polymers are inexpensive to synthesize and readily reproducible. The resulting mixed acetal polymer is blended with a photoacid generator and dissolved in a solvent to produce a chemically amplified resist composition. A process for forming a pattern comprises the steps of providing the chemically amplified resist composition, coating a substrate with the resist composition, imagewise exposing the resist coated substrate to actinic radiation, and forming a resist image by developing the resist coated substrate.

This is a division of application Ser. No. 07/059,864 filed Apr. 14,1998 pending.

FIELD OF THE INVENTION

The present invention relates to acetal derivatized polymers that haveapplications in the imaging industry as a photoresist resin forlithography and to a process for producing said acetal derivatizedpolymers.

BACKGROUND TO THE INVENTION

The wavelength of light for lithography has been reduced into the deepultraviolet (DUV) range to produce the feature size necessary forcurrent and future electronics devices. The electronics industry isdeveloping new resists that are tailored to the DUV range. One suchresist class is chemically amplified resists.

The main components of chemically amplified resist formulations are aphotoacid generator compound, a polymer resin and a solvent capable ofdissolving the photogenerator and the resin. For many positivechemically amplified resists, the polymer resin contains acid labilegroups which makes the polymer resin insoluble in an aqueous developer.Upon irradiation, the photoacid generator compound produces an acidwhich cleaves the acid labile groups resulting in a polymer resin thatis aqueous soluble. Chemically amplified resists have generated a greatdeal of interest and there are numerous patents available discussingthese compositions such as, for example, U.S. Pat. Nos. 5,069,997;5,035,979; 5,670,299; 5,558,978; 5,468,589; and 5,389,494.

One group of polymers which can be used as resins in chemicallyamplified resists are acetal derivatized polymers. The alkali solubilityof phenolic resins are greatly inhibited by converting the hydroxylgroups to acetal groups. Typically, acetal phenolic resins are producedby reacting a phenolic resin with a vinyl ether in the presence of anacid catalyst.

The acetal resins are then formulated with a photoacid generatorcompound and solvent to form a chemically amplified resist product. Uponirradiation, the generated acid cleaves the acetal groups, and aphenolic resin is created which is soluble in an aqueous developer.

One problem with producing acetal derivatized polymers is that currentlythere are only a very limited number of bulk vinyl ethers that can beused to produce the acetals. It is possible to generate other acetalfunctionalities by synthesizing intermediates, but this would require aseries of reactions which makes the overall process for producing acetalpolymers relatively complicated, expensive, and unlikely to bereproducible. Thus, the limited number of bulk vinyl ethers severelyconstrains the use of acetal polymers because only a small number ofacetal groups can be readily and inexpensively generated.

It would be advantageous to be able to generate reproducibly andeconomically a large variety of acetal groups on polymers. Variousresist properties such as alkaline solubility, etch resistance, filmshrinkage, temperature stability, adhesion, sensitivity can be alteredby choosing appropriate acetal functionalities. Furthermore, if morethan one acetal group can be readily generated on the polymer, thiswould provide further ability to tailor the polymer resin to a specificapplication. For example, one acetal group may be used to increase thesensitivity, while another acetal group may be used to increase the etchresistance. The host of applications for acetal polymers can be greatlyexpanded if a large variety of acetal groups on the polymers can beproduced readily.

The present inventors have developed a reproducible process for readilyproducing a wide variety of acetal derivatized polymers.

It is another object of this invention to provide a new, inexpensive,reproducible process for generating a large variety of acetalderivatized polymers that have applications as resins for photoresists.

It is a further object of this invention to provide a process forgenerating a large variety of acetal derivatized polymers based on mixedacetals. A still further object of this invention is to provide avariety of mixed acetals derivatized polymers that have applications asresins for photoresist. Yet another object of this invention is toprovide new photoresist compositions containing mixed acetal derivatizedpolymers and the use of such new photoresist compositions inphotolithography imaging processes to produce microelectronic devices.The present invention has many important advantages over the prior art.First, the present invention provides a new class of polymers based onmixed acetals. Desired properties of the polymer resin can be tailoredby choosing among appropriate acetal functionalities. Also, the relativeproportions of the different acetals in the polymer can be readilyvaried by changing the relative proportions of reagents in thefeedstock. Changing the proportion of the mixed acetals can furthertailor the properties of the polymer resin. In addition, thereproducibility of the mixed acetal polymers compositions are excellent.Reproducible polymer compositions are very important in order to producecommercially viable resist formulations because the properties of theresist must not change from batch to batch. Furthermore, the mixedacetal process is relatively inexpensive because intermediates neededfor the reaction are commercially available and only one synthesisreaction is required to produce the final acetal polymer. Previously, anumber of synthesis reactions would generally be required to produce thefinal single acetal polymer if the acetal group was not from one of thereadily available vinyl ethers.

The present invention also provides many additional advantages whichshall become apparent as described below.

SUMMARY OF THE INVENTION

The present invention readily generates a large variety of acetalderivatized polymers in a relatively simple, inexpensive, andreproducible manner. Also, a new class of polymers based on mixedacetals are produced by this invention. The acetal polymer can then beblended with a photoacid generator in a solvent to formulate achemically amplified resist composition which is used in the productionof electronics devices. The large variety of acetal derivatized polymerswhich can be produced by this process will make it easier to alter thevarious lithographic resist properties by choosing appropriate acetalfunctionalities tailored for a specific application.

The general process for generating an acetal resin according to thepresent invention comprises the steps of providing a polymer with one ormore monomer units, wherein at least one of the monomer units containone or more pendant hydroxyl group; and reacting said polymer with avinyl ether of the formula R₇ R₆ C═CH--OR₁ and an alcohol of the formulaR₂ OH in the presence of an acid catalyst; wherein R₁ is a linear,branched or cyclic alkyl group preferably having 1 to 10 carbon atoms, alinear, branched or cyclic haloalkyl group preferably having 1 to 10carbon atoms, an aralkyl group or a substituted phenylmethylene havingthe general structure; ##STR1## wherein each R₉ and R₁₀ are the same orindependently a hydrogen or an alkyl group having 1 to 6 carbons; R₂ isa linear, branched or cyclic alkyl group preferably having 1 to 10carbon atoms, a linear, branched or cyclic halogenated alkyl grouppreferably having 1 to 10 carbon atoms, or an aromatic group or asubstituted phenylmethylene having the general structure ##STR2##wherein R₉ and R₁₀ are as defined above; R₁ and R₂ are different fromeach other; R₆ and R₇ are the same or independently a hydrogen, alinear, branched or cyclic alkyl group preferably having 1 to 10 carbonatoms, a linear, branched or cyclic haloalkyl group preferably having 1to 10 carbon atoms, an aryl group, an aralkyl group, a substitutedhaloaryl, alkoxyaryl or alkylaryl group, or a combination of R₆ and R₇being able to form an alkylene chain, an alkyl substituted alkylenechain, or an oxyalkylene chain.

A more specific process for producing acetal derivatized polymersutilizes a phenolic based polymer. The phenolic based polymer is reactedwith a vinyl ether and an alcohol in the presence of an acid catalyst toproduce a polymer with mixed acetals from both the vinyl ether and thealcohol. One such acetal reaction of the phenolic based polymer(polyhydroxystyrene) is represented by the monomer units of equation 1.##STR3## Equation 1 wherein R is a hydrogen, an alkyl group preferablyhaving 1 to 6 carbon atoms, an alkoxy group preferably having 1 to 6carbon atoms or an acetoxy group; R₁ is a linear, branched or cyclicalkyl group preferably having 1 to 10 carbon atoms, a linear, branchedor cyclic haloalkyl group preferably having 1 to 10 carbon atoms, anaralkyl group or a substituted phenylmethylene having the generalstructure ##STR4## wherein each R₉ and R₁₀ are the same or independentlya hydrogen or an alkyl group having 1 to 6 carbons; R₂ is a linear,branched or cyclic alkyl group preferably having 1 to 10 carbon atoms, alinear, branched or cyclic halogenated alkyl group preferably having 1to 10 carbon atoms, an aromatic group or a substituted phenylmethylenehaving the general structure ##STR5## wherein R₉ and R₁₀ are as definedabove; R₁ and R₂ are not the same; R₆ and R₇ are the same orindependently a linear, branched or cyclic alkyl group preferably having1 to 10 carbon atoms, a linear, branched or cyclic haloalkyl grouppreferably having 1 to 10 carbon atoms, an aryl group, an aralkyl group,a substituted haloaryl, alkoxyaryl or alkylaryl group, or a combinationof R₆ and R₇ being able to form an alkylene chain, an alkyl substitutedalkylene chain, or an oxyalkylene chain; R₁₁ is hydrogen or methyl ;x=0.6 to 1; y=0 to 0.4; and x+y=1.0; 0<a≦0.6; 0<b≦0.6; 0<a+b≦0.6;0.4≦c+d<1.0; and a+b+c+d=1.0; and where all numbers represent molefractions.

The process of this invention provides a new class of polymers based onmixed acetals which are prepared in-situ with one reaction. The mixedacetal polymers are inexpensive to synthesize and readily reproducible.

The invention also provides that the resulting mixed acetal polymer isblended with a photoacid generator and dissolved in a solvent to producea chemically amplified resist composition. Other components to theresist composition can be added such as dyes, surfactants andstabilizers, and the like.

This invention further provides a process for forming a pattern whichcomprises the steps of providing the chemically amplified resistcomposition with the mixed acetal polymer, coating a substrate with theresist composition, imagewise exposing the resist coated substrate toactinic radiation, and forming a resist image by developing the resistcoated substrate. Further processing of the substrate may take placeafter the formation of the resist image.

Other and further objects, advantages and features of the presentinvention will be understood by reference to the followingspecification.

DETAILED DESCRIPTION AND EMBODIMENTS

The process for producing the acetal derivatized polymers, thephotoresist compositions containing the acetal polymer, and the processsteps for producing the resist image in accordance with the presentinvention are as follows.

The process for producing the acetal derivatized polymers comprisesreacting a hydroxyl based polymer with a vinyl ether and alcohol in thepresence of an acid catalyst to produce a polymer with acetals from boththe vinyl ether and the alcohol. The preferred hydroxyl based polymersare phenolic based polymers and the more preferable phenolic basedpolymers are novolaks and polyhydroxystyrene (PHS). One such reaction ofthe phenolic based polymer PHS is represented by the aforementionedequation 1. ##STR6## Equation 1 wherein; R is a hydrogen, an alkyl grouppreferably having 1 to 6 carbon atoms, an alkoxy group preferably having1 to 6 carbon atoms or an acetoxy group; R₁ is a linear, branched orcyclic alkyl group preferably having 1 to 10 carbon atoms, a linear,branched or cyclic haloalkyl group preferably having 1 to 10 carbonatoms, an aralkyl group, or a substituted phenylmethylene having thegeneral structure ##STR7## wherein each R₉ and R₁₀ are the same orindependently a hydrogen or an alkyl group having 1 to 6 carbons; R₂ isa linear, branched or cyclic alkyl group preferably having 1 to 10carbon atoms, a linear, branched or cyclic halogenated alkyl grouppreferably having 1 to 10 carbon atoms, an aromatic group, or asubstituted phenylmethylene having the general structure ##STR8##wherein R₉ and R₁₀ are as defined above; R₁ and R₂ are not the same; R₆and R₇ are the same or independently a hydrogen, a linear, branched orcyclic alkyl group preferably having 1 to 10 carbon atoms, a linear,branched or cyclic haloalkyl group preferably having 1 to 10 carbonatoms, an aryl group, an aralkyl group, a substituted haloaryl,alkoxyaryl or alkylaryl group, or a combination of R₆ and R₇ being ableto form an alkylene chain, an alkyl substituted alkylene chain, or anoxyalkylene chain; R₁₁ is hydrogen or methyl; x=0.6 to 1; y=0 to 0.4;and x+y=1.0; 0<a≦0.6; 0<b≦0.6; 0<a+b≦0.6; 0.4≦c+d<1.0; and a+b+c+d=1.0;and where all numbers represent mole fractions.

Any suitable vinyl ethers may be used for the acetalization process. Thealkyl groups represented by R₁ include, but are not limited to, methyl,ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,dodecyl, and the like. The halogens of the haloalkyl represented by R₁include chlorine, bromine, fluorine, and iodine. The aralkyl groupsrepresented by R₁ include, but are not limited to, benzyl, phenethyl,phenylpropyl, methylbenzyl, methylphenethyl and ethylbenzyl. Thepreferable R₁ groups are secondary and tertiary alkyls preferably havingfrom 1 to 6 carbon atoms. The more preferable R₁ groups are tertiaryalkyls. The most preferred R₁ is tertiary-butyl.

The alkyl groups represented by R₆ and R₇ include, but are not limitedto, methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, and the like. The halogens of the haloalkylrepresented by R₆ and R₇ include chlorine, bromine, fluorine, andiodine. The aralkyl groups represented by R₆ and R₇ include, but are notlimited to, benzyl, phenethyl, phenylpropyl, methylbenzyl,methylphenethyl and ethylbenzyl. Suitable examples of the combination ofR₆ and R₇ forming a chain are cyclohexane, methylcyclohexane and pyran.The preferred R₆ and R₇ are hydrogen.

The more preferred vinyl ethers are the readily available bulk vinylethers; ethyl vinyl ether, tertiary-butyl vinyl ether and cyclohexylvinyl ether.

Also, any suitable alcohol may be used for the reaction. The alkylgroups represented by R₂ include, but are not limited to, methyl, ethyl,propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,dodecyl, and the like. The halogens of the haloalkyl represented by R₂include chlorine, bromine, fluorine, and iodine. The aromatic grouprepresented by R₂ include, but are not limited to, phenyl, benzyl,phenethyl, phenylpropyl, naphthyl, napthyl ethyl, methylbenzyl,methylphenethyl and ethylbenzyl. Preferred alcohols are2,2,3,3-tetrafluoro propyl alcohol, cyclohexyl ethyl alcohol,(1R)-(-)-nopol, benzyl alcohol, phenethyl alcohol, 1-naphthol,2-naphthol and naphthyl ethanol.

The alkyl group represented by R include, but are not limited to,methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, and the like. The alkoxy group represented by Rinclude, but are not limited to methoxy, ethoxy, propoxy, butoxy, amoxy,hexoxy, heptoxy, octoxy, nonoxy, decoxy, undecoxy, dodecoxy, and thelike. The preferred R groups are hydrogen or tertiary-butyl.

The preferred % acetalization ((a+b)/(a+b+c))×100 is about 10% to about35%. The preferred percent R₂ incorporated in the polymer is about 80%to less than 100% of the total acetalization.

Although the embodiments are based on polyhydroxystyrene, (PHS), whichis typically used as a resin for DUV lithography, it should be notedthat any hydroxyl containing polymer may be used to produce mixedacetals using this process because the acetalization occurs at thehydroxyl site. For example, instead of having a phenolic resin, acyclohexanol or a mixed cyclohexanol-phenolic based polymer may be used.The acetal groups will be generated at the hydroxyl site, and a mixedacetal polymer based on cyclohexane will result.

Other suitable polymers for this process are novolaks which aretypically used as resins for photoresist. The hydroxyl sites of novolaksmay be also be acetalized with the present process.

It should also be noted that each repeating unit of the polymer maycontain one or .20 more hydroxyl groups. For example, the polymer maycontain a dihydroxy phenyl repeating unit. The acetalization reactionmay occur on none, either, or both hydroxyl sites depending on theoverall degree of acetalization.

The overall degree of acetalization of the hydroxyl sites is controlledby the amount of vinyl ether used in the feedstock. The relative ratiosof R₁ and R₂ in the acetal derivatized polymer can be controlled by therelative amounts of vinyl ether and alcohol respectively used in thefeedstock. The proportion of R₂ acetals in the polymer increasesrelative to R₁ as the amount of alcohol R₂ OH used in the feedstockincreases.

In a typical synthesis procedure, an hydroxyl based polymer or copolymeris dissolved in any suitable solvent or solvent mixture. The solventpresent should be inert under the reaction conditions. Suitable solventsmay include aromatic hydrocarbons, chlorinated hydrocarbons, esters, andethers such as tetrahydrofuran, (THF), 1,4-dioxane, methylene chloride,propylene glycol monomethyl ether acetate, (PGMEA), and dimethoxyethane.Preferred solvents for the reaction are THF and PGMEA.

To such a solvent, the vinyl ether and the alcohol are added at roomtemperature. The desired concentration of polymer or copolymer dissolvedin the solvent is about 10 weight percent to about 60 weight percent.The amounts of vinyl ether may vary from about 0.01 mole percent toabout 60 mole percent of the total moles of phenolic hydroxyl groups.The preferable range of vinyl ether is about 15 mole percent to about 40mole percent. The amount of alcohol used may vary from about 0.01 molepercent to about 110 mole percent of the amount of vinyl ether used.

An acid catalyst is added and the reaction mixture is allowed to stirfor about 4 to about 24 hours. The preferred reaction time is about 20hours. Any suitable acid catalyst may be used for the reaction such ashydrochloric acid, sulfuric acid, para-toluene sulfonic acid andpyridinium-para-toluene sulfonate. The preferred acid catalyst ispyridinium-para-toluene sulfonate. The acid catalyst may be added inamounts ranging from about 0.001 weight percent to about 3.0 weightpercent based on the weight of the polymer. The preferred amount of acidcatalyst added is about 0.005 weight percent. The acid catalyst isnormally quenched with an organic or inorganic base. The acetal derivedhydroxystyrene based polymer is isolated by any suitable polymerisolation procedure such as by precipitation in a non-solvent.

It will be appreciated that although this invention is described byreacting vinyl ether and alcohol with a hydroxyl based polymer in thepresence of an acid catalyst, the acetal polymers can also be generatedby first reacting the vinyl ether and alcohol with monomers and thenpolymerizing the subsequent monomer mixture. For example, a preferredprocess would be to provide hydroxystyrene monomers and react saidmonomers with vinyl ether and alcohol in the presence of an acidcatalyst to form mixed acetal monomers. The mixture of monomers can thenbe polymerized by any suitable polymerization process, such as usingfree radical initiation, to form the mixed acetal polymers. One skilledin the art of polymerization could choose the appropriate polymerizationprocess.

In an another embodiment of the invention, the structure of the backbonein the polymer reactant may be modified to include other monomers suchas acrylates, methacrylates and itaconates to form mixed acetalcopolymers, such as the following monomer units according to equation 2:##STR9## Equation 2 wherein R, R₁, R₂, R₆, R₇ and R₁₁ are defined above;R₁ and R₂ are not the same; R₃ is a hydrogen atom, methyl or ethylgroup, or a group having the formula --CH₂ --COOR₈ ; R₄ and R₈ are thesame or independently a linear, branched or cyclic alkyl grouppreferably having 1 to 12 carbon atoms, a linear, branched or cyclichalogenated alkyl group preferably having 1 to 12 carbon atoms, anaromatic group or a linear or cyclic α-alkoxyalkyl group; x=0.6 to 1;y=0 to 0.4; z=0 to 0.4; 0<a≦0.6; 0<b≦0.6; 0<a+b≦0.6; 0.4≦c+d+e<1.0;a+b+c+d+e=1.0; and where all numbers represent mole fractions.

The alkyl groups represented by R₄ and R₈ include, but are not limitedto, methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, and the like. The halogens of the haloalkylrepresented by R₄ include chlorine, bromine, fluorine, and iodine. Thearomatic groups represented by R₄ include, but are not limited to,benzyl, phenethyl, phenylpropyl, methylbenzyl, methylphenethyl andethylbenzyl. Preferred R₄ groups are methyl, ethyl, 2-hydroxy ethyl,propyl, isopropyl, n-butyl, t-butyl, 2-ethyl hexyl, andtetrahydropyranyl.

In a further embodiment of the invention, the acetal-derivatizedhydroxyl containing polymers, such as the hydroxystyrene based polymersand copolymers of equation 1 and 2, may further be modified toincorporate a tertiary butoxycarbonyloxy (t-BOC) ortertiary-butyloxycarbonyl-methoxy (BOCMe) functional groups. The t-BOCfunctional group can be introduced by reacting the polymers orcopolymers of equation 1 and 2 with di-tertiary-butyl dicarbonate in thepresence of any suitable organic or inorganic base such as dimethylamino pyridine. Similarly, BOCMe functional group can be introduced byreacting the polymers or copolymers of equation 1 and 2 withtertiary-butyl bromoacetate. With these modifications, the monomer unitsof the derivative polymer of hydroxystyrene would be as follows:##STR10## wherein R, R₁, R₂, R₃, R₄, R₆, R₇, R₈ and R₁₁ are as definedabove; R₁ and R₂ are not the same; R₅ is a valence bond or methylene;0<a≦0.6; 0<b≦0.6; f=0 to 0.10; 0<a+b+f≦0.6; 0.4≦c+d+e<1.0;a+b+c+d+e+f=1.0; and where all numbers represent mole fractions.

A preferred embodiment of the invention is the acetal polymer of formulaV wherein R₁ is tertiary-butyl, R₂ is phenethyl, R₆ and R₇ are hydrogen,R₁₁ is hydrogen, d is 0, e is 0, f is 0, 0.1≦((a+b)/(a+b+c))≦0.35;0.8≦(b/(a+b))<1.

Another preferred embodiment of the invention is the acetal polymer offormula V wherein R₁ is tertiary-butyl, R₂ is phenethyl, R₆ and R₇ arehydrogen, R₁₁ is hydrogen, e is 0, f is 0, d is 0.05 to 0.25; R istertiary-butyl; 0.1≦((a+b)/(a+b+c))≦0.35; 0.8≦(b/(a+b))<1.

Still another preferred embodiment of the invention is the acetalpolymer of formula V wherein R₁ is tertiary-butyl, R2 is phenethyl, R₆and R₇ are hydrogen, R₁₁ is hydrogen, e is 0, f is 0, d is 0.05 to 0.25;R is hydrogen; 0.1≦((a+b)/(a+b+c))≦0.35; 0.8≦(b/(a+b))<1.

A further preferred embodiment of the invention is the acetal polymer offormula V wherein R₁ is tertiary-butyl, R₂ is cyclohexyl ethyl, R₆ andR₇ are hydrogen , R₁₁ is hydrogen, e is 0, f is 0, d is 0.05 to 0.25; Ris tertiary-butyl; 0.1≦((a+b)/(a+b+c))≦0.35; 0.8≦(b/(a+b))<1.

A still further preferred embodiment of the invention is the acetalpolymer of formula V wherein R₁ is tertiary-butyl, R₂ is phenethyl, R₆and R₇ are hydrogen , R₁₁ is hydrogen, d is 0, f is 0, 0<e≦0.4; R₃ ishydrogen; R₄ is tertiary-butyl; 0.1 ≦((a+b)/(a+b+c))≦0.35;0.8≦(b/(a+b))<1.

Another preferred embodiment of the invention is the acetal polymer ofthe formula V wherein R₁ is tertiary-butyl, R₂ is phenethyl, R₆ and R₇are hydrogen, R₁₁ is hydrogen, d is 0, 0<f≦0.08, e is 0; R₅ is a valencebond; 0.1≦((a+b)/(a+b+c))≦0.35; 0.8≦(b/(a+b))<1.

The invention further relates to the formulation of photoresistcompositions comprising a mixed acetal derivatized polymer as producedabove, a photoacid generator and a solvent capable of dissolving boththe acetal derivatized polymer and the photoacid generator. Thepreferred acetal polymers for the photoresist compositions are thosethat were previously described in the preferred acetal polymerembodiments above.

Any suitable photoacid generator compounds may be used in thephotoresist composition. The photoacid generator compounds are wellknown and include, for example, onium salts such as diazonium,sulfonium, sulfoxonium and iodonium salts, and disulfones. Suitablephotoacid generator compounds are disclosed, for example, in U.S. Pat.No. 5,558,978 and. U.S. Pat. No. 5,468,589 which are incorporated hereinby reference.

Suitable examples of photoacid generators are phenacylp-methylbenzenesulfonate, benzoin p-toluenesulfonate,α-(p-toluene-sulfonyloxy)methylbenzoin3-(p-toluenesulfonyloxy)-2-hydroxy-2-phenyl-1-phenylpropyl ether,N-(p-dodecylbenzenesulfonyloxy)-1,8-naphthalimide andN-(phenyl-sulfonyloxy)-1,8-napthalimide.

Other suitable compounds are o-nitrobenzaldehydes which rearrange onactinic irradiation to give o-nitrosobenzoic acids such as1-nitrobenzaldehyde and 2,6-nitrobenzaldehyde, α-haloacylphenones suchas α,α,α-trichloroacetophenone andp-tert-butyl-α,α,α-trichloroacetophenone, and sulfonic esters ofo-hydroxyacylphenones, such as 2-hydroxybenzophenone methanesulfonateand 2,4-hydroxybenzophenone bis(methanesulfonate).

Still other suitable examples of photoacid generators aretriphenylsulfonium bromide, triphenylsulfonium chloride,triphenylsulfonium iodide, triphenylsulfonium hexafluorophosphate,triphenylsulfonium hexafluoroarsenate, triphenylsulfoniumhexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate,diphenylethylsulfonium chloride, phenacyldimethylsulfonium chloride,phenacyltetrahydrothiophenium chloride,4-nitrophenacyltetrahydrothiopheniumn chloride and4-hydroxy-2-methylphenylhexahydrothiopyrylium chloride.

Further examples of suitable photoacid generators for use in thisinvention are bis(p-toluenesulfonyl)diazomethane, methylsulfonylp-toluenesulfonyldiazomethane,1-cyclo-hexylsulfonyl-1-(1,1-dimethylethylsulfonyl)diazometane,bis(1,1-dimethylethylsulfonyl)diazomethane,bis(1-methylethylsulfonyl)diazomethane,bis(cyclohexylsulfonyl)diazomethane,1-p-toluenesulfonyl-1-cyclohexylcarbonyldiazomethane,2-methyl-2-(p-toluenesulfonyl)propiophenone,2-methanesulfonyl-2-methyl-(4-methylthiopropiophenone, 2,4-methyl-2-(p-toluenesulfonyl)pent-3-one,1-diazo-1-methylsulfonyl-4-phenyl-2-butanone,2-(cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane,1-cyclohexylsulfonyl-1cyclohexylcarbonyldiazomethane,1-diazo-1-cyclohexylsulfonyl-3,3-dimethyl-2-butanone,1-diazo-1-(1,1-dimethylethylsulfonyl)-3,3dimethyl-2-butanone,1-acetyl-1-(1-methylethylsulfonyl)diazomethane,1-diazo-1-(p-toluenesulfonyl)-3,3-dimethyl-2-butanone,1-diazo-1-benzenesulfonyl-3,3-dimethyl-2butanone,1-diazo-1-(p-toluenesulfonyl)-3-methyl-2-butanone, cyclohexyl2-diazo-2-(p-toluenesulfonyl)acetate, tert-butyl2-diazo-2-benzenesulfonylacetate,isopropyl-2-diazo-2-methanesulfonylacetate, cyclohexyl2-diazo-2-benzenesulfonylacetate, tert-butyl 2diazo-2-(p-toluenesulfonyl)acetate, 2-nitrobenzyl p-toluenesulfonate,2,6-dinitrobenzyl p-toluenesulfonate, 2,4-dinitrobenzylp-trifluoromethylbenzenesulfonate.

Other suitable examples of photogenerators arehexafluorotetrabromo-bisphenol A,1,1,1-tris(3,5-dibromo-4-hydroxyphenyl)ethane andN-(2,4,6-tribromophenyl)-N'-(p-toluenesulfonyl)urea.

More preferably, the photoacid generators can be chosen from thefollowing compounds: ##STR11##

The photoacid generator compound is typically employed in the amounts ofabout 0.0001 to about 20% by weight of polymer solids and morepreferably about 1% to about 10% by weight of polymer solids.

The choice of solvent for the photoresist composition and theconcentration thereof depends principally on the type of functionalitiesincorporated in the acetal polymer, the photoacid generator, and thecoating method. The solvent should be inert, should dissolve all thecomponents in the photoresist, should not undergo any chemical reactionwith the components and should be re-removable on drying after coating.Suitable solvents for the photoresist composition may include ketones,ethers and esters, such as methyl ethyl ketone, methyl isobutyl ketone,2-heptanone, cyclopentanone, cyclehexanone, 2-methoxy-1-propyleneacetate, 2-methoxyethanol, 2-ethoxyothanol, 2-ethoxyethyl acetate,1-methoxy-2-propyl acetate, 1,2-dimethoxy ethane ethyl acetate,cellosolve acetate, propylene glycol monoethyl ether acetate, methyllactate, ethyl lactate, methyl pyruvate, ethyl pyruvate, methyl3-methoxypropionate, ethyl 3-methoxypropionate, N-methyl-2-pyrrolidone,1,4-dioxane, ethylene glycol monoisopropyl ether, diethylene glycolmonoethyl ether, diethylene glycol monomethyl ether, diethylene glycoldimethyl ether, and the like.

In an additional embodiment, base additives may be added to thephotoresist composition. The purpose of the base additive is to scavengeprotons present in the photoresist prior to being irradiated by theactinic radiation. The base prevents attack and cleavage of the acidlabile groups by the undesirable acids thereby increasing theperformance and stability of the resist. The percentage of base in thecomposition should be significantly lower than the photoacid generatorbecause it would not be desirable for the base to interfere with thecleavage of the acid labile groups after the photoresist composition isirradiated. The preferred range of the base compounds, when present, isabout 3% to about 50% by weight of the photoacid generator compound.Suitable examples of base additives are 2-methylimidazole,triisopropylamine, 4-dimethylaminopryidine, 4,4'-diaminodiphenyl ether,2,4,5 triphenyl imidazole and 1,5-diazobicyclo[4.3.0]non-5-ene.

Dyes may be added to the photoresist to increase the absorption of thecomposition to the actinic radiation wavelength. The dye must not poisonthe composition and must be capable of withstanding the processconditions including any thermal treatments. Examples of suitable dyesare fluorenone derivatives, anthracene derivatives or pyrenederivatives. Other specific dyes that are suitable for photoresistcompositions are described in U.S. Pat. No. 5,593,812.

The photoresist composition may further comprise conventional additivessuch as adhesion promoters and surfactants. A person skilled in the artwill be able to choose the appropriate desired additive and itsconcentration.

The invention further relates to a process for forming a pattern on asubstrate which comprises the following process steps: application of aphotoresist coating comprising one of the compositions described aboveto the substrate; imagewise exposure of the coating to actinicradiation; treatment of the coating with an alkaline aqueous developeruntil the areas of the coating which have been exposed to the radiationdetach from the substrate and an imaged photoresist structured coatingremains on the substrate.

The photoresist composition is applied uniformly to a substrate by knowncoating methods. For example the coatings may be applied byspin-coating, dipping, knife coating, lamination, brushing, spraying,and reverse-roll coating. The coating thickness range generally coversvalues of about 0.1 to more than 10 μm. After the coating operation, thesolvent is generally removed by drying. The drying step is typically aheating step called soft bake where the resist and substrate are heatedto a temperature of about 50° C. to about 150° C. for about a fewseconds to about a few minutes; preferably for about 5 seconds to about30 minutes depending on the thickness, the heating element and end useof the resist.

The photoresist compositions are suitable for a number of different usesin the electronics industry. For example, it can be used aselectroplating resist, plasma etch resist, solder resist, resist for theproduction of printing plates, resist for chemical milling or resist inthe production of integrated circuits. The possible coatings andprocessing conditions of the coated substrates differ accordingly.

For the production of relief structures, the substrate coated with thephotoresist composition is exposed imagewise. The term `imagewise`exposure includes both exposure through a photomask containing apredetermined pattern, exposure by means of a computer controlled laserbeam which is moved over the surface of the coated substrate, exposureby means of computer-controlled electron beams, and exposure by means ofX-rays or UV rays through a corresponding mask.

Radiation sources which can be used are all sources which emit radiationin which the photoacid generator is sensitive. Examples are argon ion,krypton ion, electron beams and x-rays sources.

The process described above for the production of relief structurespreferably comprises, as a further process measure, heating of thecoating between exposure and treatment with the developer. With the aidof this heat treatment, known as "post-exposure bake", virtuallycomplete reaction of the acid labile groups in the polymer resin withthe acid generated by the exposure is achieved. The duration andtemperature of this post-exposure bake can vary within broad limits anddepend essentially on the functionalities of the polymer resin, the typeof acid generator and on the concentration of these two components. Theexposed resist is typically subjected to temperatures of about 50° C. toabout 150° C. for a few seconds to a few minutes. The preferred postexposure bake is from about 80° C. to 130° C. for about 5 seconds toabout 300 seconds

After imagewise exposure and any heat treatment of the material, theexposed areas of the photoresist are removed by dissolution in adeveloper. The choice of the particular developer depends on the type ofphotoresist; in particular on the nature of the polymer resin or thephotolysis products generated. The developer can comprise aqueoussolutions of bases to which organic solvents or mixtures thereof mayhave been added. Particularly preferred developers are aqueous alkalinesolutions. These include, for example, aqueous solutions of alkali metalsilicates, phosphates, hydroxides and carbonates, but in particular oftetra alkylammonium hydroxides, and more preferably tetramethylammoniumhydroxide (TMAH). If desired, relatively small amounts of wetting agentsand/or organic solvents can also be added to these solutions.

After the development step, the substrate carrying the resist coating isgenerally subjected to at least one further treatment step which changessubstrate in areas not covered by the photoresist coating. Typically,this can be implantation of a dopant, deposition of another material onthe substrate or an etching of the substrate. This is usually followedby the removal of the resist coating from the substrate typically by anoxygen plasma etch or a wet solvent strip.

This invention is explained below in further detail with references toexamples, which are not by way of limitation, but by way ofillustration.

Examples 1 and 2 below illustrate the synthesis procedure involved ingenerating the acetal polymers.

EXAMPLE 1

Synthesis of Mixed phenethyl and tertiary-butyl acetals ofpolyhydroxystyrene

A mixture of 100 ml of tetrahydrofuran (THF) and 30 g of powderedpolyhydroxystyrene (PHS) was added to a 250 ml three-necked flaskequipped with a temperature probe, an overhead mechanical stirrer and anitrogen inlet. The mixture stirred for 30 minutes to form a homogeneoussolution before 5.0 g of tertiary butyl vinyl ether, 4.8 g of phenethylalcohol and 140 mg of solid pyridinium-para-toluene sulfonate was added.A brief exotherm was observed followed by a temperature rise of 23° to27° C. The solution was allowed to stir at 23° C. for 20 hours before 4g of triethylamine solution (prepared by dissolving 2.31 g oftriethylanine in 200 g of TBF) was added to the reaction mixture toquench the acid. The reaction mixture was stirred for additional 30minutes. The polymer solution was drop-wise added to 1000 ml ofde-ionized water under vigorous stirring. The precipitated solid polymerwas isolated by filtration. The polymer was washed two times with 250 mlof de-ionized water. The polymer was dried under vacuum at 60° C. for 18hours.

EXAMPLE 2

Synthesis of Mixed phenethyl and tertiary-butyl acetals ofpolyhydroxystyrene (Alternative in-situ synthesis process)

A mixture of 140.6 g of propylene glycol monomethyl ether acetate(PGMEA) and 30 g of powdered PHS was added to a 250 ml three-neckedflask equipped with a temperature probe, an overhead mechanical stirrerand a nitrogen inlet. The mixture was stirred for 30 minutes to form ahomogeneous solution. The mixture was then heated to 66° C. and vacuumwas applied to the solution to distill 12 g of the solvent. The solutionwas allowed to cool to room temperature under nitrogen atmosphere and5.0 g of tertiary-butyl vinyl ether, 4.8 g of phenethyl alcohol and 140mg of solid pyridinium para-toluene sulfonate was added to the solution.A brief exotherm was observed followed by a temperature rise of 23° C.to 27° C. The solution was allowed to stir at 23° C. for about 20 hoursbefore 4 g of triethylamine solution (prepared by dissolving 2.81 g oftriethylamine in 200 g of THF) was added to the reaction mixture toquench the acid. The reaction mixture was stirred for additional 30minutes. The polymer solution was transferred to a 250 ml separatoryfunnel and washed with 115 g of acetone, 115 g of hexanes and 47 g ofde-ionized water. The mixture was stirred briefly for 5 minutes andallowed to separate into two layers. The lower aqueous layer wasdiscarded. The top organic layer was subjected to two more washings. Thetop organic layer was transferred to a 500 ml round-bottom, three-neckedflask. The flask was equipped with a temperature probe, an overheadstirrer and a vacuum distillation assembly. The flask was placed on aheating mantle and the organic volatiles from the polymer solution wereremoved by atmospheric distillation at about 70° C. The final traces oflow volatile solvents were removed by applying vacuum. The remainingpolymer solution was diluted to a solid content of about 30 weightpercent.

EXAMPLES 3-19

Following the synthesis procedures described in Example 1 and 2, a widevariety of acetal blocked polyhydroxystyrene (PHS) based polymers andcopolymers were synthesized. The degree of acetalization (DA) wascontrolled by varying the amount of vinyl ether. The proportion of R₂ inthe polymer was controlled by adjusting the vinyl ether/alcohol ratio.The %R₂ is calculated by the formula (b/(a+b+c))×100.

The acetal polymers are shown in Table I with the indicatedpolydispersity (PD). Total degree of acetalization (DA %) was determinedby ¹³ C-NMR and the amount of R₂ rated was determined by ¹ H-NMR. R₆ andR₇ for each of the vinyl ethers are hydrogen.

                  TABLE I                                                         ______________________________________                                                                        R.sub.1 /R.sub.2                                Exam- Description  R.sub.2 (mole) % %                                         ple of Polymer R.sub.1 (Alcohol) attempted R.sub.2 DA                       ______________________________________                                         3    Polymer A  t-butyl  --    --     --   31                                   PHS; MW =                                                                     12,000                                                                        PD = 1.04                                                                     4 Polymer A t-butyl Phenethyl  1/0.75 22 29                                   5 Polymer A t-butyl Phenethyl 1/0.5 10.4 22                                   6 Polymer A cyclo- Phenethyl 1/0.5 22 26                                       hexyl                                                                        7 Polymer B t-butyl Phenethyl 1/0.5 10 20                                     Poly(styrene-                                                                 cohydroxy                                                                     styrene);                                                                     % styrene =                                                                   17%                                                                           Mw = 9,000;                                                                   PD = 1.5                                                                      8 Polymer B t-butyl Phenethyl  1/0.75 17.8 24                                 9 Polymer C t-butyl Phenethyl 1/0.8 19.8 20                                   Poly(tertiary-                                                                butyl styrene-                                                                co-hydroxy                                                                    styrene) %                                                                    t-butyl                                                                       styrene = 7%                                                                  Mw = 12,000;                                                                  PD = 1.9                                                                     10 Polymer C t-butyl phenethyl 1/0.8 14.6 18                                  11 Polymer A t-butyl 2,2,3,3-  1/0.25 8 29                                       tetrafluoro                                                                   propyl                                                                        (TFP)                                                                      12 Polymer A t-butyl Naphthyl  1/0.25 9.5 31                                     ethyl                                                                      13 Polymer A t-butyl Naphthyl 1/0.5 9.7 23                                       ethyl                                                                      14 Polymer A t-butyl 1- 1/0.5 14.2 33                                            cyclohexyl                                                                    ethyl                                                                      15 Polymer A t-butyl 1-  1/0.25 7.9 31                                           cyclohexyl                                                                    ethyl                                                                      16 Polymer C t-butyl 1- 1/0.8 14 18                                              cyclohexyl                                                                    ethyl                                                                      17 Polymer A t-butyl (1R)-(-)- 1/0.5 9.9 30                                      nopyl                                                                      18 Polymer A t-butyl (1R)-(-)-  1/0.25 5.5 28                                    nopyl                                                                      19 Polymer D t-butyl phenethyl 1/0.8 23 30                                     poly(t-butyl                                                                  acrylate-co-                                                                  hydroxy                                                                       styrene)                                                                      % t-butyl                                                                     acrylate = 30%                                                               *20  Polymer A t-butyl phenethyl 1/1   17 17                                ______________________________________                                         *Analysis by .sup.1 HNMR indicated that all the acetal moieties in the        polymer were substituted with phenethyl groups.                          

EXAMPLE 21-24

Reproducibility of synthesis procedures

To test the reproducibility of the synthesis procedures described above,four experiments were run under identical conditions according toexamples 1 and 2; wherein R₁ is tert-butyl, R₂ is phenethyl, and R₆ andR₇ are hydrogen. The vinyl ether and alcohol mole percentages are basedon the total moles of phenolic hydroxyl groups in the polymer. Table IIsummarizes the results of the experiments.

                  TABLE II                                                        ______________________________________                                                               Mole %                                                                              mole %                                              Polymer  R.sub.1 in R.sub.2 in  % R.sub.2                                    Exam- from  feed- feed- DA % incorp.                                          ple Table I Amount stock stock .sup.13 C-NMR .sup.1 H-NMR                   ______________________________________                                        21    Polymer A                                                                              30 g    30    22.5  23     16                                    22 Polymer A 30 g 30 22.5 23.8 15                                             23 Polymer A 30 g 30 22.5 24.9 15.8                                           24 Polymer B 30 g 30 22.5 24 17.8                                           ______________________________________                                    

The results of Table II show that the DA% and the percent of the R₂acetal present in the PHS based polymer is highly reproducible varyingby less than ±1%.

EXAMPLE 25

Synthesis of a polyhydroxystyrene based polymer with mixed phenethyl andtertiary-butyl acetals and a tertiary butoxycarbonyl-oxy (t-BOC) group

To a round bottom flask containing 100 g of 30 weight percent solutionof polyhydroxystyrene based polymer of mixed phenethyl and t-butylacetal in 1-methoxy-2-propyl acetate produced according to example 21,5.0 mg of dimethyl amino pyridine was added. The mixture was stirred byan overhead stirrer for about 30 minutes before 2.72 g ofdi-tertiary-butyl dicarbonate was added. The solution was allowed tohomogenize for about 15 minutes. The mixture was then stirred for about32 hours under nitrogen conditions until the reaction was completed asmeasured by FT IR.

EXAMPLES 26-29

The examples in Table III below shows how resist properties can bemodified by utilizing different acetal functionalities. Specifically,the glass transition temperature (Tg) and the alkaline solubilityproperties (Tc) were altered by using a variety of alcohols togetherwith t-butyl vinyl ether and polyhydroxystyrene (PHS) polymers. Tc isthe length of time in seconds for a 1.0 μm film of the polymer to beremoved from a substrate in 0.5 N TMAH. The control PHS used a lessconcentrated TMAH solution (0.26 N) so that the time of removal could beaccurately measured.

                  TABLE III                                                       ______________________________________                                                               R.sub.1 /R.sub.2                                            (mole) % mole                                                              Exam-  R.sub.2 in feed R.sub.2 in % Tg Tc                                     ple R.sub.1 (alcohol) stock polymer DA (° C.) (sec)                  ______________________________________                                        Control                                                                             --       --      0     0      0   165   4                                 (PHS)       (0.26N                                                                   TMAH)                                                                  26 t-butyl  -- -- 0 34 115 80                                                 (PHS)                                                                         27 t-butyl 2,2,3,3,- 1/0.25 8 29  83 89                                       (PHS)  tetra                                                                    fluoro                                                                        propyl                                                                        alcohol                                                                     28 t-butyl phenethyl 1/0.5  10.4 22 116 98                                    (PHS)                                                                         29 t-butyl naphthyl 1/0.25 9.5 31  90 444                                     (PHS)  ethyl                                                                ______________________________________                                    

EXAMPLES 30-35

Formulating, Coating, Baking, Exposure, Post Exposure Baking, andDeveloping of the Photoresists

The following general procedure was followed for the formulation anddevelopment of the positive photoresist.

Photoresist formulations were prepared by blending the followingcomponents in amber colored glass bottles.

Acetal derivatized hydroxystyrene based polymer solution in1-methoxy-2-propylene acetate (30% solution) (8.7 g)

Photoacid generator (PAG) (formula VIII) (0.27 g)

2,4,5 triphenyl imidazole (0.0675 g) (Base additive)

1,5-diazobicyclo[4.3.0]non-5-ene (0.045 g) (Base additive)

FLUORAD FC430 (fluoroaliphatic polymeric esters) (Surfactant)

Solvent: 2-methoxy-1-propylene acetate (15.9 g)

When all the components had dissolved, the resist samples were microfiltered directly into clean bottles.

Silicon wafers were spin coated by applying 3 ml of photoresistformulations to static four inch wafers. The wafers were then spun togive a uniform film thickness of around 7600 Å. These photoresist coatedwafers were then soft baked (SB) to remove the residual solvents. Thesoftbaked photoresist coated wafers were then exposed using 248 nmwavelength light on an ISI XLS 0.53 NA stepper. After completion ofexposure, the wafers were subjected to a post exposure bake (PEB).Following the PEB, the wafers were puddle or spray-developed using a0.26 N tetramethyl ammonium hydroxide aqueous developer. A de-ionizedwater rinse was applied for 20 seconds while spinning, followed by drynitrogen gas to dry the wafers.

Each imaged photoresist-coated substrate was evaluated for severalimportant properties, such as optimum photospeed (Eopt), standing wavesand equal line/space pair resolution (res.). The degree of standingwaves were qualitatively evaluated on a scale of 1 to 5 where 1 is poorand 5 is excellent. The % film shrinkage was calculated by measuring thethickness before exposure T1, and the thickness of the film afterexposure T2. The % film shrinkage is the difference in thickness beforeand after the exposure and is calculated by the formula((T1-T2)/T1)×100. All the components in the photoresist are the same asexample 30 except for the acetal polymers. The results are summarized inTable IV.

                  TABLE IV                                                        ______________________________________                                               Polymer                                                                   described E.sub.opt Resolution Standing % Film                               Example in Table I (mJ/cm.sup.2) μm wave Shrinkage                       ______________________________________                                        30     Example 3 12       0.2    1      11                                      31 Example 4 24 0.175 4-5 2.6                                                 32 Example 7 21 0.2 5 0.6                                                     33 Example 15 24 0.175 4  0.79                                                34 Example 10 25 0.175 5 <1.0                                                 35 Example 25 32 0.175 -- <1.0                                              ______________________________________                                    

The results show that all the photoresist compositions have excellentresolution of 0.2 μm and below with good sensitivity. Most compositionsalso have good film shrinkage and standing wave properties.

The foregoing is illustrative 6f the present invention and is notconstrued as limiting thereof. The invention is defined by the followingclaims with equivalents of the claims to be included therein.

What is claimed is:
 1. A process for generating a mixture of acetalmonomers comprising the steps of:providing a monomer containing one ormore hydroxyl groups; reacting said monomer containing one or morehydroxyl groups with a vinyl ether of the formula R₆ R₇ C═CH--OR₁ and analcohol of the formula R₂ OH in the presence of an acid catalyst;whereinR₁ is a linear, branched or cyclic alkyl group, a linear, branched orcyclic haloalkyl group, or an aralkyl group, or a substitutedphenylmethylene having the general structure ##STR12## wherein each R₉and R₁₀ are the same or independently a hydrogen or an alkyl grouphaving 1 to 6 carbons; R₂ is a linear, branched or cyclic alkyl group, alinear, branched or cyclic halogenated alkyl group, an aromatic group,or a substituted phenylmethylene having the general structure; ##STR13##wherein R₉ and R₁₀ are as defined above; R₆ and R₇ are the same orindependently a hydrogen, a linear, branched or cyclic alkyl group, alinear, branched or cyclic haloalkyl group, an aryl group, an aralkylgroup a substituted haloaryl, alkoxyaryl or alkylaryl group, or acombination of R₆ and R₇ being able to form an alkylene chain, an alkylsubstituted alkylene chain, or an oxyalkylene chain.
 2. The process ofclaim 1 wherein said monomer containing one or more hydroxyl groups is aphenolic monomer.
 3. The process of claim 2 wherein said monomer ishydroxystyrene.
 4. A process for producing a mixed acetal polymercomprising the steps of:providing a mixture of acetal monomers producedby the process of claim 1; and polymerizing said mixture of acetalmonomers to form a mixed acetal polymer.
 5. The process of claim 4wherein said mixture of acetal monomers comprises a mixture ofhydroxystyrene based mixed acetal monomers.